Water-insoluble monoazo-dyestuffs



United States Patent WATER-INSOLUBLE MONOAZO-DYESTUFFS Helmut Gies, Hofheim, Taunus, and Helmut Lindner and Arthur Siebert, Frankfurt am Main, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main, Germany, a corporation of Germany No Drawing. Filed June 11, 1963, Ser. No. 286,922 Claims priority, applicl rtion 1Germany, June 22, 1962,

Claims. 61. 260-207) The present invention relates to water-insoluble monoazo-dyestuffs and to a process for preparing them; more particularly it relates to water-insoluble monoazo-dyestuffs of the general formula 0 CHz-CHzOY /C Hz-C H2 0 Y MGM N 'CH2CHzOY NO: NHZ

OCHz-CHzOY CHg-CHgOY o; NHZ

in which X represents a hydrogen, chlorine or bromine atom, Y represents a hydrogen atom or an acyl radical of low molecular weight, and Z represents an acyl radical of low molecular Weight, can be prepared by diazotizing amines of the general formula in which X has the meaning indicated above, and coupling them in the acid range with coupling components of the general formula oonl-omoy CHz-CHzOY I -CHs-CEHOY NHZ in which Y and Z have the meanings indicated above.

Suitable diazo components are the 2,4-dinitraniline and derivatives thereof substituted in 6-position by chlorine or bromine. As coupling components there may be used 2-dihydroxy ethylamino-4-acetarnino-fi-hydroxy-phenetole and acylation products thereof.

The novel products dye as dispersion dyestuif semior fully synthetic fibers, such as acetate silk or polyethylene terephthalate violet to blue shades and in admixture with other dyestuffs are suitable for the production of black shades. The dyeings possess a good fastness to light and an excellent fastness to thermofixation.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto.

Example 1 3i) grams A mol) of 2-dihydroxy-ethylamino-4- acetamino-fi-hydroxy-phenetole (obtained by reacting 1 3,250,762 Patented May 10, 1966 mol of 2 amino-4-nitro-B-hydroxy-phenetole with 2 mols of ethylene oxide, reducing the nitro group and acetylating it With lmol of acetic anhydride) are dissolved in grams of dioxane, and after the addition of 100 grams of acetic anhydride and 5 grams of pyridine the solution obtained is .boiled under reflux for 30 minutes. After cooling the reaction mixture is poured on 500 grams of ice. Into this mixture is run, while vigorously stirring, the solution of 18.3 grams mol) of diazotized 2,4- dinitraniline in 200 milliliters of glacial acetic acid. The pH-val-ue is then adjusted to 3 by adding sodium acetate solution, and subsequently the Whole is diluted With Water to a volume of 3000 milliliters. The coupling product, which precipitated in the form of black-blue crystals, is filtered off after 2 hours, washed thoroughly with water and finally dried. '50 grams of a dyestuff of the formula NH-C OC H3 are obtained Which dyes polyethylene terephthalate fibers violet-blue shades. to light and an excellent fastness to sublimation.

Example 2 dyes polyethylene terephthalate fabric deep blue shades. The dyeings posses .a very good fastness to light and an excellent fastness to sublimation.

A dyestuff of similar dyeing properties is obtained, when using instead of 26.2 grams of 2,4-dinitro-6- bromaniline 21.7 grams of 2,4-dinitro-6-chloraniline.

Example 3 A diazo solution prepared in usual manner from 21.7 grams 0/ mole) of 2,4-dinitro-6-chloraniline is run into a solution of 30 grains /10 mol) of Z-dihydroxy-ethylaminor4-acetamino-B-hydroxy-phenetole in 100 grams of glacial acetic acid. The volume is then made up to 3 liters by diluting with water and the pH-v'alue is adjusted to 3 by adding an acetate solution. The precipitated dyestuff is filtered off, Washed and dried. 50 grams of a' dyestuff are obtained which in an aqueous dispersion dyes polyethylene terephthalate fabric blue sh'ades. The dyeings possess a good fastness to light and an excellent fastness to thcrmofixation.

When replacing for the preparation of the diazo compound the 21.7 grams of 2,4-dinitro-fi-chloraniline by 26.2 grams of 2,4-dinitro-6-brom.aniline and proceeding as described above, a dye-stuff of similar shade is obtained which also possesses excellent fastness properties.

Example 4 30 grams (V mol) of 2-dihydroxy-ethylarnino-4-acet- The dyeings possess a good fastness amino-,B-hydroxy-phenetole are dissolved in 100 grams of dioxane. The solution obtained is boiled under reflux for 30 minutes after the addition of 20.4 grams mol) of acetic anhydnide. After cooling, the reaction mixture is poured on 500 grams of ice. The diazo compound prepared in usual manner irorn 26.2 grams rnol) of 2,4-di'nit-ro-6-bromaniline is run, while vigorously stir-ring, into the thus obtained solution of the diaceto-hydroxy compound of 2-dihydroxy-ethylamino-4-acetarrniino-fi-hydroxy-phenetole. The pH-value is then adjusted to 3 by adding an acetate solution and the whole is worked up as described in Example 1. The dyestutf obtained dyes polyethylene terephthalate blue shades. The dyeings possess a good fastness to light .and an excelent fastness to sublimation.

A dyestuif of similar dyeing properties and similar shade is obtained, when using instead of the diazo cornpound prepared from 26.2 grams of dinitro-G-bromaniline the diazo solution prepared from 21.7 grams mol) of 2,4-dinitro-6-chloraniline.

Example 5 30 grams mol) of Z-dihydroxy-ethy1amino-4- acetam-ino-B-hydroxy-phenetole dissolved in 100 grams of dioxane are acetylated as described in Example 4 with 10.2 grams mol) of acetic anhydride and the reaction mixture is poured on ice. The diazo compound of 21.7 grams of 2,4-dinitro-6-chloraniline disolved in 250 milliliters o-f glacial acetic acid is then run into the mixture, subsequently the whole is diluted with water to a volume of 3 liters and the pH-value is adjusted to 3 by adding sodium acetate solution. The precipitated dyestufi is worked up as described in Example 1. It dyes polyethylene terephthalate fibers blue shades. The dyein gs possess a good fastness to light and excelent thermal fastness properties.

A dyestufi of almost analogous 'fiastness properties and very similar shade is obtained when using the diazo compound prepared from 26.2 grams moi) of 2,4- dinitro-6- bromraniline instead of the diazo compound prepared from 2,4-dinitro-6 chloroaniline.

Example 6 30 grams A moi) of Z-dihydroxy-ethylaminolacetamino-fl-hydroxy phenetole are reacted as described in Example 4 with 20.4 grams A mol) of acetic anhydride. A diazo compound prepared in usual manner from 18.3 grams mol) of 2,4dinitraniline dissolved in 200 grams of glacial acetic acid are added to the reaction mixture to which ice had been added. The dyestuff which precipitated after the addition of acetate solution and water is isolated in the above-described manner. It dyes polyethylene terephthalate in an aqueous dispersion violet shades. The dyeings possess a good fastness to light and excellent thermal fastness properties.

Example 7 A diazo solution prepared in usual manner from 18.3 grams (V mol) of 2,4-dinitraniline in 200 milliliters of glacial acetic acid are added to a solution of the reaction product described in Example 5 and obtained from 30 grams mol) of 2-dihydroxy-ethylamino-4-acetamino- 8-hydroxy-phenetole and 10.2 grams (34 mol) of acetic anhydride to which ice had been added. The whole is Worked up as described in Example 5. The dyestuff obtained dyes polyethylene terephthalate bluish violet shades. The dyeimgs possess a good fiastness to light and an excellent fastnes to thenmofixation. 7

We claim:

1. The water-insoluble monoazo-dyestulfs having the fonmula X OCHaCHz-OY CHPCHQOY N02 NHZ in which X represents a member of the group consisting of hydrogen, chlorine and bromine, Y represents a member of the group consisting of hydrogen and lower a1- kanoyl, and Z represents a lower alkanoyl group.

2. A water-insoluble dyestulf of the formula OzN- wherein X is a member selected from the group consisting of hydrogen, chlorine, and bromine and Y is a member selected from the group consisting of hydrogen and acetyl.

3. The water-insoluble monazo-dyestutf having the formula NH-C O-CHa 5-. The water-insoluble monoazo-dyestuff having the formula CHARLES B. PARKER, Primary Examiner. IRVING MARCUS, Examiner.

R EYNOLD J. FINNEGAN, DONALD PAPUGA,

Assistant Examiners. 

1. THE WATER-INSOLUBLE MONOAZO-DYESTUFFS HAVING THE FORMULA 